Solid battery



INVENTOR W/'///0m d Pau/f w. J. PAULI v soLID BATTERY Filed Nov. so, 1955 Sept. 9,. 1958 United States Patent O 2,851,510 SOLID BATTERY William J. Pauli, Washington, D. C. Application November 30, 1955, Serial No. 550,221

i 1 claim. (ci. 13s-103) (Granted under 'Itle 35, U. S. Code (1952), sec. 266) They have exceptionally long shelf life, as the is in a solid state. Because, in an ion exresin, all the current is carried by either the posithe negative ions, no concentration polarization change tive or occurs.

An object of the invention is to provide a battery having long shelf life.

provide a battery with constant open circult voltage, low internal resistance, and good low temperature operation.

Further objects of the invention are to achieve the above in a cheap and simple manner with a device that is sturdy and easy to manufacture.

The specific nature of the invention as well as other objects and advantages thereof will clearly appear from the following ydescription and drawings in which:

Fig. 1 is an enlarged cross sectional View of a iirst species of the cell of the invention.

Fig. 2 is an enlarged cross sectional view of a second species of the cell.

Fig. 3 is an enlarged cross sectional View of a third species ofthe cell.

Fig. 4 is an enlarged cross sectional view of a modication of the third species.

Fig. 5 is an enlarged cross sectional view of a fourth species of the cell.

Fig. 6 is an enlarged fragmentary view in cross section illustrating the construction of the cell as incorporated in a battery.

Fig. 7 is an enlarged cross sectional view of a battery employing the cells of the invention.

pressure. Caton exchange resins are well known and include sulfonated polystyrene, for example. Before assembly the hydrogen lons of sheet 14 have been replaced various well known techniquesfor example by soaking the sheet in a solution of a zinc salt. Sheet 16 has been similarly treated to replace its hydrogen ions with silver ions. Sheets 14 and 16 are hydrated with water or solvated with an organic liquid with a high dielectric constant such as glycerine or formamide.

When an electrical load is connected between electrodes 10 and 12 a current is generated by a process that involves zinc leaving electrode 10 to displace `zinc ions in resin sheet 14. Zinc ions from sheet 14 simultaneously migrate to sheet 16, displacing silver ions; the silver ions from sheet 16 plate out on electrode 12.

Of course, other combinations of metals could be used Apolymer dissolved in toluene for the electrodes 10 and 12, for example, magnesium and gold. In this species each resin sheet 14 and 16 has mobile ions ofthe metal it contacts.

The thickness of resin membranes or sheets 14 and 16 is not critical. thickness have been used the surface of .the zinc plate 10. The sheets 14 and 16 may be ion exchange-resins in the pure state or may consist of particles of such resin in a suitable binder. terial is commercially available wherein particles of an ion exchange .resin are embedded in the thermoplastic binder polyethylene. Solvent type binders may also be used. For example, particles of an ion exchange resin may be mixed with vinyl-'chloride vnylidene-chloride coand this mixture spread on a plate for the toluene to evaporate.

Figs. 6 and 7 show the construction of a battery incorporating cells using ion exchange resins. A basic element strip ,60 is -prepared by plating a silver ribbon 62 on one side with zinc 64 forming a bimetal strip 66. On the side of strip 66 a mobile silver ion is applied. Good resinare readily obtained. The battery 70 is starting with a plate of zinc 72, followed The bottom and top single sociated sheets of resin resin 68, 69, would be surplusage ity in mass production.

The shelf life Fig. 2 shows a variation wherein a cell comprises a cadmium plate 20, a single resin sheet 22 and an oxide plate 24. The resin sheet 22 has a mobile hydrogen ion. The oxide plate 24 may, for example, be nickel with an oxidized surface or vanadium with a surface of vanadium pentoxide. The action is that cadmium from plate 20 replaces hydrogen in the resin at the junction of plate 20 and sheet 22. At the junction of sheet 22 and plate 24 the hydrogen combines with the oxygen to form Water.

Another variation shown in Fig. 3 uses a zinc plate 30, resin sheets 32 and 34, and a silver chloride plate 36. The sheet 32 is a cation exchange resin with zinc as the mobile ion, and sheet 34 is an anion exchange resin containing exchangeable chlorine ions. Plate 36 is a silver plate with a chlorized surface. The action is that plate 30 releases zinc ions to resin sheet 32 while plate 36 releases chloride ions to sheet 34. At the junction of sheets 32 and 34 the ions combine to form soluble zinc chloride.

In another modification shown in Fig. 4, a zinc plate 40, four resin sheets 42, 43, 44 and 45, and a silver. chloride plate 48 are stacked in series. Sheet 42 has mobile zinc ions; 43, hydrogen ions; 44, hydroxyl ions; and 45, chloride ions. The action is that zinc ions migrate from zinc plate 40 to the face of sheet 43 Where they displace hydrogen ions. Likewise, chlorine ions migrate from silver chloride plate 48 to the face of sheet, 4 4 where they displace hydroxyl ions. At the junction of sheets 43 and 44 the hydrogen and hydroxyl ions unite to form water.

Fig. 5 shows a cell with a zinc plate 50, resin sheets 52 and 54, and cuprous hydroxide plate 56. vSheet 52 has a mobile zinc ion and sheet 54 has a mobile hydrogen ion. Plate S6 is copper with a hydroxided surface. The action is that the migrating zinc ions displace the hydrogen ions in sheet 54. The hydrogen ions combine with hydroxyl ions at the face of plate 56 to forrn water.

It will be apparent that the embodmentsshown are only exemplary and that various modifications can be made in materials, construction and arrangement within the scope of the invention as dened in the appended claim. A t

I claim:

A battery cell comprising in combination: rst and second electrode plates, the first plate being Zinc and the second plate being silver with a chlorized surface, and first, second, third, and fourth hydrated ion exchange resin sheets interposed between said plates, said rst sheet having mobile zinc ions, said second sheet having mobile hydrogen ions, said third sheet having mobile hydroxyl ions, and said fourth sheet having mobile chloride ions, said rst sheet having one side in contact with said zinc plate and the other side in contact with one side of said second sheet, said third sheet having one side in contact with the other side of said second sheet, said fourth sheet havingv one side in contact with the other side of said third sheet, the other side of said fourth sheet being in contact with the chlorized surface of said second plate.

References Cited in the le of this patent UNITED STATES PATENTS 2,166,179 Ruben July 18, 1939 2,403,567 Wales July 9, 1946 V2,607,809 Pitzer Aug. 19, 1952 2,636,851 Juda et al Apr. 28, 1953 2,696,513 Lehovec Dec. 7, 1954 2,700,063 Manecke Ian. 18, 1955 2,707,199 Ruben Apr. 26, 1955 2,747,009 Kirkwood et al. May 22, 1956 2,762,858 Wood Sept. 11, 1956 

